Immediately after from what I've experienced is the best time. However, within a couple hours does help as well.
Basically, (IMO) if you do it anytime before you sleep -- which is the most anabolic time your body undergoes -- limiting the inflammation with the cold shower/ice bath so the body can repair itself more efficiently will work.
I've never tried working out in the morning and taking a cold shower at night, but I assume it would help as well based on this line of thought.
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